US8206520B2 - Method of forming ductile metallic glasses in ribbon form - Google Patents

Method of forming ductile metallic glasses in ribbon form Download PDF

Info

Publication number
US8206520B2
US8206520B2 US12/547,367 US54736709A US8206520B2 US 8206520 B2 US8206520 B2 US 8206520B2 US 54736709 A US54736709 A US 54736709A US 8206520 B2 US8206520 B2 US 8206520B2
Authority
US
United States
Prior art keywords
range
atomic percent
ribbon
present
melt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US12/547,367
Other languages
English (en)
Other versions
US20100092329A1 (en
Inventor
Daniel James Branagan
Brian E. MEACHAM
Alla V. Sergueeva
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanosteel Co Inc
Nano Steel Co Inc
Original Assignee
Nano Steel Co Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nano Steel Co Inc filed Critical Nano Steel Co Inc
Priority to US12/547,367 priority Critical patent/US8206520B2/en
Assigned to THE NANOSTEEL COMPANY, INC. reassignment THE NANOSTEEL COMPANY, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BRANAGAN, DANIEL JAMES, MEACHAM, BRIAN E., SERGUEEVA, ALLA V.
Publication of US20100092329A1 publication Critical patent/US20100092329A1/en
Priority to US13/532,313 priority patent/US8679267B2/en
Application granted granted Critical
Publication of US8206520B2 publication Critical patent/US8206520B2/en
Assigned to HORIZON TECHNOLOGY FINANCE CORPORATION reassignment HORIZON TECHNOLOGY FINANCE CORPORATION SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: THE NANOSTEEL COMPANY, INC.
Assigned to HORIZON TECHNOLOGY FINANCE CORPORATION reassignment HORIZON TECHNOLOGY FINANCE CORPORATION SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: THE NANOSTEEL COMPANY, INC.
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15308—Amorphous metallic alloys, e.g. glassy metals based on Fe/Ni
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15333—Amorphous metallic alloys, e.g. glassy metals containing nanocrystallites, e.g. obtained by annealing

Definitions

  • the present disclosure relates to chemistries of matter which may result in amorphous or amorphous/nanocrystalline structures which may yield relatively high strength and relatively high plastic elongation.
  • Metallic nanocrystalline materials and metallic glasses may be considered classes of materials known to exhibit relatively high hardness and strength characteristics. Due to their perceived potential, they may be considered candidates for structural applications. However, these classes of materials may also exhibit relatively limited fracture toughness associated with the relatively rapid propagation of shear bands and/or cracks which may be a concern for the technological utilization of these materials. While these materials may show adequate ductility by testing in compression, when testing in tension these materials may exhibit elongations that may be close to zero and in the brittle regime. The inherent inability of these classes of material to be able to deform in tension at room temperature may be a limiting factor for potential structural applications where intrinsic ductility may be needed to potentially avoid catastrophic failure.
  • Nanocrystalline materials may be understood to include, by definition, polycrystalline structures with a mean grain size below 100 nm. They have been the subject of widespread research since the mid-1980s when Gleiter made the argument that metals and alloys, if made nanocrystalline, may exhibit a number of appealing mechanical characteristics of potential significance for structural applications. But despite relatively attractive properties (high hardness, yield stress and fracture strength), it is well known that nanocrystalline materials may generally show a disappointing and relatively low tensile elongation and may tend to fail in an extremely brittle manner.
  • Valiev, et al. proposed that an increased content of high-angle grain boundaries in nanocrystalline materials could be beneficial to an increase in ductility.
  • relatively ductile base metals have generally been used such as copper, aluminum or zinc with some limited success.
  • Wang, et al. fabricated nanocrystalline Cu with a bimodal grain size distribution (100 nm and 1.7 ⁇ m) based on the thermomechanical treatment of severe plastic deformation. The resulting highly stressed microstructure which was only partially nanoscale was found to exhibit a 65% total elongation to failure while retaining a relative high strength.
  • Lu, et al. produced a nanocrystalline copper coating with nanometer sized twins embedded in submicrometer grained matrix by pulsed electrodeposition.
  • the relatively good ductility and high strength was attributed to the interaction of glide dislocations with twin boundaries.
  • nanocrystalline second-phase particles of 4-10 nm were incorporated into the nanocrystalline Al matrix (about 100 nm).
  • the nanocrystalline particles were found to interact with the slipping dislocation and enhanced the strain hardening rate which leads to the evident improvement of ductility.
  • enhanced tensile ductility has been achieved in a number of nanocrystalline materials such as 15% in pure Cu with mean grain size of 23 nm or 30% in pure Zn with mean grain size of 59 nm.
  • Amorphous metallic alloys i.e. metallic glasses
  • metallic glasses represent a relatively young class of materials, having been first reported in 1960 when Klement, et al., performed rapid-quenched experiments on Au—Si alloys. Since that time, there has been remarkable progress in exploring alloys compositions for glass formers, seeking elemental combinations with ever-lower critical cooling rates for the retention of an amorphous structure. Due to the absence of long-range order, metallic glasses may exhibit what is believed to be somewhat atypical properties, such as relatively high strength, high hardness, large elastic limit, good soft magnetic properties and high corrosion resistance.
  • the present disclosure relates to an iron based alloy composition.
  • the iron based alloy may include iron present in the range of 45 to 70 atomic percent, nickel present in the range of 10 to 30 atomic percent, cobalt present in the range of 0 to 15 atomic percent, boron present in the range of 7 to 25 atomic percent, carbon present in the range of 0 to 6 atomic percent; and silicon present in the range of 0 to 2 atomic percent, wherein the alloy exhibits an elastic strain of greater than 0.5% and a tensile strength of greater than 1 GPa.
  • the present disclosure relates to a method of forming an alloy including melting one or more feedstocks to form an alloy and forming ribbon from the alloy.
  • the alloy may include iron present in the range of 45 to 70 atomic percent, nickel present in the range of 10 to 30 atomic percent, cobalt present in the range of 0 to 15 atomic percent, boron present in the range of 7 to 25 atomic percent, carbon present in the range of 0 to 6 atomic percent; and silicon present in the range of 0 to 2 atomic percent.
  • the ribbon may exhibit an elastic strain of greater than 0.5% and a tensile strength of greater than 1 GPa.
  • FIGS. 1 a through 1 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6 melt-spun at 16 m/s, b) PC7E6JC melt-spun at 16 m/s, c) PC7E6JB melt-spun at 16 m/s, d) PC7E6JA melt-spun at 16 m/s, e) PC7E6J1 melt-spun at 16 m/s, and f) PC7E6J3 melt-spun at 16 m/s.
  • FIGS. 2 a through 2 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6J7 melt-spun at 16 m/s, b) PC7E6J9 melt-spun at 16 m/s, c) PC7E6H1 melt-spun at 16 m/s, d) PC7E6H3 melt-spun at 16 m/s, e) PC7E6H7 melt-spun at 16 m/s, and f) PC7E6H9 melt-spun at 16 m/s.
  • FIGS. 3 a through 3 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6HA melt-spun at 16 m/s, b) PC7E6HB melt-spun at 16 m/s, c) PC7E6HC melt-spun at 16 m/s, d) PC7E6J1H9 melt-spun at 16 m/s, e) PC7E6J3H9 melt-spun at 16 m/s, and f) PC7E6J7H9 melt-spun at 16 m/s.
  • FIGS. 4 a through 4 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6J9H9 melt-spun at 16 m/s, b) PC7E6J1HA melt-spun at 16 m/s, c) PC7E6J3HA melt-spun at 16 m/s, d) PC7E6J7HA melt-spun at 16 m/s, e) PC7E6J9HA melt-spun at 16 m/s, and f) PC7E6J1HB melt-spun at 16 m/s.
  • FIGS. 5 a through 5 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6J3HB melt-spun at 16 m/s, b) PC7E6J7HB melt-spun at 16 m/s, c) PC7E6J1HC melt-spun at 16 m/s, d) PC7E7 melt-spun at 16 m/s.
  • FIGS. 6 a through 6 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6 melt-spun at 10.5 m/s, b) PC7E6JC melt-spun at 10.5 m/s, c) PC7E6JB melt-spun at 10.5 m/s, d) PC7E6JA melt-spun at 10.5 m/s, e) PC7E6J1 melt-spun at 10.5 m/s, and 0 PC7E6J3 melt-spun at 10.5 m/s.
  • FIGS. 7 a through 7 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6J7 melt-spun at 10.5 m/s, b) PC7E6J9 melt-spun at 10.5 m/s, c) PC7E6H1 melt-spun at 10.5 m/s, d) PC7E6H3 melt-spun at 10.5 m/s, e) PC7E6H7 melt-spun at 10.5 m/s, and f) PC7E6H9 melt-spun at 10.5 m/s.
  • FIGS. 8 a through 8 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6HA melt-spun at 10.5 m/s, b) PC7E6HB melt-spun at 10.5 m/s, c) PC7E6HC melt-spun at 10.5 m/s, d) PC7E6J1H9 melt-spun at 10.5 m/s, e) PC7E6J3H9 melt-spun at 10.5 m/s, and f) PC7E6J7H9 melt-spun at 10.5 m/s.
  • FIGS. 9 a through 9 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6J9H9 melt-spun at 10.5 m/s, b) PC7E6J1HA melt-spun at 10.5 m/s, c) PC7E6J3HA melt-spun at 10.5 m/s, d) PC7E6J7HA melt-spun at 10.5 m/s, e) PC7E6J9HA melt-spun at 10.5 m/s, and f) PC7E6J1HB melt-spun at 10.5 m/s.
  • FIGS. 10 a through 10 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6J3HB melt-spun at 10.5 m/s, b) PC7E6J7HB melt-spun at 10.5 m/s, c) PC7E6J1HC melt-spun at 10.5 m/s, d) PC7E7 melt-spun at 10.5 m/s.
  • FIGS. 11 a and 11 b are images of an example of a two point bend test system; a) image of bend tester, b) close-up schematic of bending process.
  • FIG. 12 illustrates bend test data showing the cumulative failure probability as a function of failure strain for the PC7E6H series alloys melt-spun at 10.5 m/s.
  • FIG. 13 illustrates bend test data showing the cumulative failure probability as a function of failure strain for the PC7E6J series alloys melt-spun at 10.5 m/s.
  • FIG. 14 illustrates the results on the PC7E6 series alloys which have been melt-spun at 16 m/s and then bent 180° until flat.
  • FIG. 15 illustrates the results of the PC7E6 series alloys which have been melt-spun at 10.5 m/s and then bent 180° until flat.
  • FIG. 16 illustrates examples of hand bent samples of PC7E6HA which have been hand bent 180°; a) melt-spun at 10.5 m/s in a 1 ⁇ 3 atm helium environment, b) melt-spun at 10.5 m/s in a 1 atm air environment, c) melt-spun at 16 m/s in a 1 ⁇ 3 atm helium environment, d) melt-spun at 16 m/s in a 1 atm air environment, e) melt-spun at 30 m/s in a 1 ⁇ 3 atm helium environment, and f) melt-spun at 30 m/s in a 1 atm air environment.
  • FIG. 17 illustrates DTA curves of the PC7E6HA alloy showing the presence of glass to crystalline transformation peak(s); a) melt-spun at 10.5 m/s in a 1 ⁇ 3 atm helium environment (also showing melting behavior), b) melt-spun at 10.5 m/s in a 1 atm air environment, c) melt-spun at 16 m/s in a 1 ⁇ 3 atm helium environment, d) melt-spun at 16 m/s in a 1 atm air environment, e) melt-spun at 30 m/s in a 1 ⁇ 3 atm helium environment, and f) melt-spun at 30 m/s in a 1 atm air environment.
  • FIG. 18 illustrates X-ray diffraction scans of the PC7E6J1 sample melt-spun at 16 m/s; wherein the top curve illustrates the free side and the bottom curve illustrates the wheel side.
  • FIG. 19 illustrates X-ray diffraction scans of the PC7E6J1 sample melt-spun at 10.5 m/s; wherein the top curve illustrates the free side, and the bottom curve illustrates the wheel side.
  • FIGS. 20 a through 20 c illustrate SEM backscattered electron micrographs of the PC7E6; a) low magnification showing the entire ribbon cross section, note the presence of isolated points of porosity, b) medium magnification of the ribbon structure, c) high magnification of the ribbon structure.
  • FIGS. 21 a through 21 c illustrate SEM backscattered electron micrographs of the PC7e6HA; a) low magnification showing the entire ribbon cross section, b) medium magnification of the ribbon structure, note the presence of isolated points of crystallinity, c) high magnification of the ribbon structure.
  • FIG. 22 illustrates a stress strain curve for the PC7E6HA alloy melt-spun at 16 m/s.
  • FIG. 23 illustrates a SEM secondary electron image of the PC7E6HA alloy melt-spun at 16 m/s and then tensile tested.
  • FIG. 24 illustrates a stress strain curve for the PC7E7 alloy melt-spun at 16 m/s.
  • FIG. 25 illustrates a SEM secondary electron image of the PC7E7 alloy melt-spun at 16 m/s and then tensile tested. Note the presence of the crack on the right hand side of the picture (black) and the presence of multiple shear bands indicating a large plastic zone in front of the crack tip.
  • the present disclosure relates to an iron based alloy, wherein the iron based glass forming alloy may include, consist essentially of, or consist of about 45 to 70 atomic percent (at %) Fe, 10 to 30 at % Ni, 0 to 15 at % Co, 7 to 25 at % B, 0 to 6 at % C, and 0 to 2 at % Si.
  • the level of iron may be 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, and 70 atomic percent.
  • the level of nickel may be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 and 30 atomic percent.
  • the level of cobalt may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 atomic percent.
  • the level of boron may be 7, 8, 9, 10, 11, 12, 13 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 and 25 atomic percent.
  • the level of carbon may be 0, 1, 2, 3, 4, 5 and 6 atomic percent.
  • the level of silicon may be 0, 1 and 2 atomic percent.
  • the glass forming chemistries may exhibit critical cooling rates for metallic glass formation of less than 100,000 K/s, including all values and increments in the range of 10 3 K/s to 10 5 K/s.
  • Critical cooling rate may be understood as a cooling rate that provides for formation of glassy fractions within the alloy composition.
  • the iron based glass forming alloy may result in a structure that may consist primarily of metallic glass. That is at least 50% or more of the metallic structure, including all values and increments in the range of 50% to 99%, in 1.0% increments, may be glassy. Accordingly, it may be appreciated that little ordering on the near atomic scale may be present, i.e., any ordering that may occur may be less than 50 nm.
  • the iron based alloy may exhibit a structure that includes, consists essentially of, or consists of metallic glass and crystalline phases wherein the crystalline phases may be less than 500 nm in size, including all values and increments between 1 nm and 500 nm in 1 nm increments.
  • the alloys may include, consist essentially of, or consist of iron present in the range of 46 at % to 69 at %; nickel present in the range of 12 at % to 27 at %; optionally cobalt, which if present, may be present in the range of 2 at % to 15 at %; boron present in the range of 12 at % to 16 at %; optionally carbon, which if present, may be present in the range of 4 at % to 5 at %; optionally silicon, which if present, may be present in the range of 0.4 at % to 0.5 at %.
  • the alloys may include the above alloying elements at 100 at % and impurities may be present in a range of 0.1 at % to 5.0 at %, including all values and increments therein. Impurities may be introduced by, among other mechanisms, feedstock compositions, processing equipment, reactivity with the environment during processing, etc.
  • the alloys may be produced by melting one or more feedstock compositions, which may include individual elements or elemental combinations.
  • the feedstocks may be provided as powders or in other forms as well.
  • the feedstocks may be melted by radio frequency (rf) induction, electric arc furnaces, plasma arc furnaces, or other furnaces or apparatus using a shielding gas, such as an argon or helium gas.
  • rf radio frequency
  • the feedstocks Once the feedstocks have been melted, they may be formed into ingots shielded in an inert gas environment.
  • the ingots may be flipped and remelted to increase and/or improve homogeneity.
  • the alloys may then be meltspun into ribbon having widths up to about 1.25 mm.
  • Melt spinning may be performed at, for example, tangential velocities in the range of 5 to 25 meter per second, including all values and increments therein.
  • the ribbon may have a thickness in the range of 0.02 mm to 0.15 mm, including all values and increments therein.
  • Other processes may be used as well, such as twin roll casting or other relatively rapid cooling processes capable of cooling the alloys at a rate of 100,000 K/s or less.
  • the above alloys may exhibit a density in the range of 7.70 grams per cubic centimeter to 7.89 grams per cubic centimeter, +/ ⁇ 0.01 grams per cubic centimeter, including all values and increments therein.
  • the alloys may exhibit one or more glass to crystalline transition temperatures in the range of 410° C. to 500° C., including all values and increments therein, measured using DSC (Differential Scanning Calorimetry) at a rate of 10° C. per minute.
  • Glass to crystalline transition temperature may be understood as a temperature in which crystal structures begin formation and growth out of the glassy alloy.
  • the primary onset glass to crystalline transition temperature may be in the range of 415° C. to 474° C.
  • the secondary onset glass to crystalline transition temperature may be in the range of 450° C. to 488° C., including all values and increments therein, again measured by DSC at a rate of 10° C. per minute.
  • the primary peak glass to crystalline transition temperature may be in the range of 425° C. to 479° C. and the secondary peak glass to crystalline transition temperature may be in the range of 454° C. to 494° C., including all values and increment therein, again measured by DSC at a rate of 10° C. per minute.
  • the enthalpy of transformation may be in the range of ⁇ 40.6 J/g to ⁇ 210 J/g, including all values and increments therein.
  • DSC may be performed under an inert gas to prevent oxidation of the samples, such as high purity argon gas.
  • the above alloys may exhibit initial melting temperatures in the range of 1060° C. to 1120° C.
  • Melting temperature may be understood as the temperature at which the state of the alloy changes from solid to liquid.
  • the alloys may exhibit a primary onset melting temperature in the range of 1062° C. to 1093° C. and a secondary onset melting temperature in the range of 1073° C. to 1105° C., including all values and increments therein, as measured by DSC at a rate of 10° C. per minute.
  • the primary peak melting temperature may be in the range of 1072° C. to 1105° C. and the secondary peak melting temperature may be in the range of 1081° C. to 1113° C., including all values and increments therein, measured by DSC at a rate of 10° C. per minute.
  • DSC may be performed under an inert gas to prevent oxidation of the samples, such as high purity argon gas.
  • the iron based glass forming alloys may result in a structure that exhibits a Young's Modulus in the range of 119 to 134 GPa, including all values and increments therein.
  • Young's Modulus may be understood as the ratio of unit stress to unit strain within the proportional limit of a material in tension or compression.
  • the alloys may also exhibit an ultimate or failure strength in the range of greater than 1 GPa, such as in the range of 1 GPa to 5 GPa, such as 2.7 GPa to 4.20 GPa, including all values and increments therein. Failure strength may be understood as the maximum stress value.
  • the alloys may exhibit an elastic strain 0.5% or greater, including all values and increments in the range of 0.5 to 4.0%.
  • Elastic strain may be understood as the change in a dimension of a body under a load divided by the initial dimension in the elastic region.
  • the alloy may also exhibit a tensile or bending strain greater than 2% and up to 97%, including all values and increments therein.
  • the tensile or bending strain may be understood as the maximum change in a dimension of a body under a load divided by the initial dimension.
  • the alloy may also exhibit a combination of the above properties, such as a failure strength greater than 1 GPa and a tensile or bending strain greater than 2%.
  • the resulting alloys may also exhibit amorphous fractions, nanocrystalline structures and/or microcrystalline structures.
  • microcrystalline may be understood to include structures that exhibit a mean grain size of 500 nm or less, including all values and increments in the range of 100 nm to 500 nm.
  • Nanocrystalline may be understood to include structures that exhibit a mean grain size of below 100 nm, such as in the range of 50 nm to 100 nm, including all values and increments therein.
  • Amorphous may be understood as including structures that exhibit relatively little to no order, exhibiting a mean grain size, if grains are present, in the range of less than 50 nm.
  • the ingots were melted in a 1 ⁇ 3 atm helium atmosphere using RF induction and then ejected onto a 245 mm diameter copper wheel which was traveling at tangential velocities which varied from 5 to 25 m/s.
  • the resulting PC7E6 series ribbon that was produced had widths which were typically up to ⁇ 1.25 mm and thickness from 0.02 to 0.15 mm.
  • the density of the alloys in ingot form was measured using the Archimedes method in a specially constructed balance allowing weighing in both air and distilled water.
  • the density of the arc-melted 15 gram ingots for each alloy is tabulated in Table 2 and was found to vary from 7.70 g/cm 3 to 7.89 g/cm 3 .
  • Experimental results have revealed that the accuracy of this technique is + ⁇ 0.01 g/cm 3 .
  • the two-point bending method for strength measurement was developed for thin, highly flexible specimens, such as optical fibers and ribbons.
  • the method involves bending a length of tape (fiber, ribbon, etc.) into a “U” shape and inserting it between two flat and parallel faceplates.
  • One faceplate is stationary while the second is moved by a computer controlled stepper motor so that the gap between the faceplates can be controlled to a precision of better than ⁇ 5 ⁇ m with an ⁇ 10 ⁇ m systematic uncertainty due to the zero separation position of the faceplates ( FIG. 11 ).
  • the stepper motor moves the faceplates together at a precisely controlled specified speed at any speed up to 10,000 ⁇ m/s. Fracture of the tape is detected using an acoustic sensor which stops the stepper motor. Since for measurements on the tapes, the faceplate separation at failure varied between 2 and 11 mm, the precision of the equipment does not influence the results.
  • ⁇ f 1.198 ⁇ ( d D - d ) ( 1 )
  • ⁇ f 1.198 ⁇ ⁇ E ⁇ ( d D - d ) ( 2 )
  • d is the tape thickness
  • D is the faceplate separation at failure.
  • Young's modulus was measured from nanoindentation testing and was found to vary from 119 to 134 GPa for the PC7E6 series alloys. As indicated earlier, for the samples not measured, Young's Modulus was estimated to be 125 GPa.
  • the shape of the tape between the faceplates is an elastica which is similar to an ellipse with an aspect ratio of ⁇ 2:1. The equation assumes elastic deformation of the tape.
  • Equation #3 The strength data for materials is typically fitted to a Weibull distribution as shown in Equation #3:
  • m is the Weibull modulus (an inverse measure of distribution width) and ⁇ 0 is the Weibull scale parameter (a measure of centrality, actually the 63% failure probability).
  • m is a dimensionless number corresponding to the variability in measured strength and reflects the distribution of flaws. This distribution is widely used because it is simple to incorporate Weibull's weakest link theory which describes how the strength of specimens depends on their size.
  • FIGS. 12 and 13 two point bend results are shown giving the cumulative failure probability as a function of failure strain for the PC7E6H and PC7E6J series alloys, respectively, which have been melt-spun at 10.5 m/s. Note that every data point in these Figures represents a separate bend test and for each sample, 17 to 25 measurements were done. In Table 6, the results on these 10.5 m/s bend test measurements are tabulated including Young's Modulus (GPA and psi), failure strength (GPA and psi), Weibull Modulus, average strain (%), and maximum strain (%). The Young's modulus of 125 GPa was used for bend testing calculations of strength which is an average value for such types of alloys.
  • the Weibull Modulus was found to vary from 2.97 to 8.49 indicating the presence of macrodefects in some of the ribbons causing premature failure.
  • the average strain in percent was calculated based on the sample set that broke during two-point bend testing. The average strain ranged from 1.52 to 2.15%.
  • the maximum strain in percent during bending was found to vary from 2.3% to 3.36%. Failure strength values were calculated from 2.87 to 4.20 GPa.
  • the strain may be in the range of ⁇ 57% to ⁇ 97% strain in the tension side of the ribbon.
  • the results show a varied behavior including brittle, bendable on one side along entire length (not counting occasion localized areas containing defects), bendable in isolated spots only in one direction, and bendable on both sides (i.e. wheel and free sides).
  • FIG. 14 there is a wide composition regime with respect to nickel and cobalt, where the samples can be bent in both directions.
  • the thick ribbons i.e. those processed at 10.5 m/s
  • no samples were found to be bendable in both directions.
  • FIG. 15 there is a fairly narrow composition regime (i.e.
  • nickel and cobalt ratios where the ribbons are bendable flat along the entire length in one direction.
  • These Figures illustrate the effects of changing nickel and cobalt content on bending response and intrinsic elongation. Note however that by changing the base elements including boron, carbon, silicon, and iron, it is expected that the bending response can be changed and enhanced especially at the lower wheel speeds such as 10.5 m/s.
  • the as-spun ribbons were then cut and four to six pieces of ribbon were placed on an off-cut SiO 2 single crystal (zero-background holder).
  • the ribbons were situated such that either the shiny side (free side) or the dull side (wheel side) were positioned facing up on the holder.
  • a small amount of silicon powder was placed on the holder as well, and then pressed down with a glass slide so that the height of the silicon matched the height of the ribbon, which will allow for matching any peak position errors in subsequent detailed phase analysis.
  • X-ray diffraction scans were taken from 20 to 100 degrees (two theta) with a step size of 0.02 degrees and at a scanning rate of 2 degrees/minute.
  • the X-ray tube settings with a copper target were 40 kV and 44 mA.
  • X-ray diffraction scans are shown for the PC7E6J1 alloy melt-spun at 16 m/s showing the free side and wheel sides.
  • X-ray diffraction scans are shown for the PC7E6J1 alloy melt-spun at 10.5 m/s showing the free side and wheel sides.
  • SEM scanning electron microscopy
  • FIG. 21 SEM backscattered electron micrographs are shown of the PC7E6HA alloy at three different magnifications. As shown, the images show generally a featureless microstructure but in the region at medium magnification, (i.e. FIG. 21 b ), isolated points of crystallinity are found on a scale of approximately 500 nm. This may indicate that a key component in getting high elongation may be crystalline precipitates in a glass matrix.
  • the Young's Modulus was found to be 112.8 GPA with a measured tensile strength of 3.17 GPa and a total elongation of 2.9%. Note that the initial tensile testing was performed with a relatively large gauge length (23 mm) which is approximately a factor of 10 longer than what it should be based on the sample cross sectional area. Additionally, the grips were not perfectly aligned in both the horizontal and vertical directions. Thus during tensile testing, misalignment and torsional strains were occurring which limited the maximum elongation and tensile strength. In FIG. 23 , a SEM backscattered electron micrograph is shown of the PC7E6HA alloy melt-spun at 16 m/s after tensile testing.
  • the localized strain is estimated to be ⁇ 30% in the axial direction and ⁇ 98% in the longitudinal direction.
  • the Young's Modulus was found to be 108.6 GPA with a measured tensile strength of 2.70 GPa and a total elongation of 4.2%. Note that the initial tensile testing was done with an excessively large gauge length (23 mm) which is approximately a factor of 10 longer than what it should based on the sample cross sectional area. Additionally, the grips were not perfectly aligned in both the horizontal and vertical directions. Thus during tensile testing, misalignment and torsional strains were occurring which limited the maximum elongation and tensile strength. In FIG. 25 , a SEM backscattered electron micrograph is shown of the PC7E7 alloy melt-spun at 16 m/s after tensile testing.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Continuous Casting (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
  • Soft Magnetic Materials (AREA)
US12/547,367 2008-08-25 2009-08-25 Method of forming ductile metallic glasses in ribbon form Active 2030-04-12 US8206520B2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US12/547,367 US8206520B2 (en) 2008-08-25 2009-08-25 Method of forming ductile metallic glasses in ribbon form
US13/532,313 US8679267B2 (en) 2008-08-25 2012-06-25 Ductile metallic glasses in ribbon form

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9155808P 2008-08-25 2008-08-25
US12/547,367 US8206520B2 (en) 2008-08-25 2009-08-25 Method of forming ductile metallic glasses in ribbon form

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/532,313 Division US8679267B2 (en) 2008-08-25 2012-06-25 Ductile metallic glasses in ribbon form

Publications (2)

Publication Number Publication Date
US20100092329A1 US20100092329A1 (en) 2010-04-15
US8206520B2 true US8206520B2 (en) 2012-06-26

Family

ID=41797424

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/547,367 Active 2030-04-12 US8206520B2 (en) 2008-08-25 2009-08-25 Method of forming ductile metallic glasses in ribbon form
US13/532,313 Expired - Fee Related US8679267B2 (en) 2008-08-25 2012-06-25 Ductile metallic glasses in ribbon form

Family Applications After (1)

Application Number Title Priority Date Filing Date
US13/532,313 Expired - Fee Related US8679267B2 (en) 2008-08-25 2012-06-25 Ductile metallic glasses in ribbon form

Country Status (6)

Country Link
US (2) US8206520B2 (de)
EP (1) EP2327080A4 (de)
JP (1) JP5728382B2 (de)
KR (1) KR101629985B1 (de)
CA (1) CA2735450C (de)
WO (1) WO2010027813A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110108166A1 (en) * 2009-11-06 2011-05-12 The Nanosteel Company, Inc. Utilization of Amorphous Steel Sheets In Honeycomb Structures

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2741454C (en) * 2008-10-21 2019-01-08 The Nanosteel Company, Inc. Mechanism of structural formation for metallic glass based composites exhibiting ductility
AU2009313602B2 (en) * 2008-11-04 2015-08-20 The Nanosteel Company, Inc. Exploitation of deformation mechanisms for industrial usage in thin product forms
WO2011150383A2 (en) 2010-05-27 2011-12-01 The Nanosteel Company, Inc. Alloys exhibiting spinodal glass matrix microconstituents structure and deformation mechanisms
KR101860590B1 (ko) * 2010-11-02 2018-05-23 더 나노스틸 컴퍼니, 인코포레이티드 비정질 나노-물질
DE102013205597A1 (de) 2013-03-28 2014-10-02 Voith Patent Gmbh Schaber
KR20160021579A (ko) * 2014-08-18 2016-02-26 서울대학교산학협력단 고탄성 비정질 합금 유연성 기판과 그 제조방법 및 이를 이용한 전자소자
EP3321382B1 (de) 2016-11-11 2020-01-01 The Swatch Group Research and Development Ltd Co-basierte hochfeste amorphe legierung und verwendung davon
JP6401806B2 (ja) * 2017-02-14 2018-10-10 株式会社Pfu 日付識別装置、日付識別方法及び日付識別プログラム
CN106893952B (zh) * 2017-03-15 2018-08-10 常州市美格耐特非晶材料有限公司 一种用于声磁标签材料的非晶带
US11969368B2 (en) * 2017-05-12 2024-04-30 Biotyx Medical (Shenzhen) Co., Ltd. Lumen stent and preform thereof, and methods for preparing the lumen stent and preform thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4144058A (en) 1974-09-12 1979-03-13 Allied Chemical Corporation Amorphous metal alloys composed of iron, nickel, phosphorus, boron and, optionally carbon
US6077367A (en) 1997-02-19 2000-06-20 Alps Electric Co., Ltd. Method of production glassy alloy
US20020069944A1 (en) * 2000-10-05 2002-06-13 Weihs Timothy P. High performance nanostructured materials and methods of making the same
US20050263216A1 (en) 2004-05-28 2005-12-01 National Tsing Hua University Ternary and multi-nary iron-based bulk glassy alloys and nanocrystalline alloys
US20080053274A1 (en) 2005-02-11 2008-03-06 The Nanosteel Company, Inc. Glass stability, glass forming ability, and microstructural refinement
US7618499B2 (en) * 2003-10-01 2009-11-17 Johnson William L Fe-base in-situ composite alloys comprising amorphous phase
WO2010005745A1 (en) 2008-06-16 2010-01-14 The Nanosteel Company, Inc Ductile metallic glasses
WO2010048060A1 (en) 2008-10-21 2010-04-29 The Nanosteel Company, Inc. Mechanism of structural formation for metallic glass based composites exhibiting ductility

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63317645A (ja) * 1987-03-24 1988-12-26 Nippon Steel Corp 管状体補強用高耐食性非昌質合金繊維
US6093261A (en) * 1995-04-13 2000-07-25 Alliedsignals Inc. Metallic glass alloys for mechanically resonant marker surveillance systems
US6018296A (en) 1997-07-09 2000-01-25 Vacuumschmelze Gmbh Amorphous magnetostrictive alloy with low cobalt content and method for annealing same
US6359563B1 (en) * 1999-02-10 2002-03-19 Vacuumschmelze Gmbh ‘Magneto-acoustic marker for electronic article surveillance having reduced size and high signal amplitude’

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4144058A (en) 1974-09-12 1979-03-13 Allied Chemical Corporation Amorphous metal alloys composed of iron, nickel, phosphorus, boron and, optionally carbon
US6077367A (en) 1997-02-19 2000-06-20 Alps Electric Co., Ltd. Method of production glassy alloy
US20020069944A1 (en) * 2000-10-05 2002-06-13 Weihs Timothy P. High performance nanostructured materials and methods of making the same
US7618499B2 (en) * 2003-10-01 2009-11-17 Johnson William L Fe-base in-situ composite alloys comprising amorphous phase
US20050263216A1 (en) 2004-05-28 2005-12-01 National Tsing Hua University Ternary and multi-nary iron-based bulk glassy alloys and nanocrystalline alloys
US20080053274A1 (en) 2005-02-11 2008-03-06 The Nanosteel Company, Inc. Glass stability, glass forming ability, and microstructural refinement
WO2010005745A1 (en) 2008-06-16 2010-01-14 The Nanosteel Company, Inc Ductile metallic glasses
WO2010048060A1 (en) 2008-10-21 2010-04-29 The Nanosteel Company, Inc. Mechanism of structural formation for metallic glass based composites exhibiting ductility

Non-Patent Citations (40)

* Cited by examiner, † Cited by third party
Title
ASTM E 2456-06, Standard Terminology Relating to Nanotechnology, 2007.
Chen et al., "Extraordinary Plasticity of Ductile Bulk Metallic Glasses," PRL 96, 245502 (2006).
Chen, "Free-volume-induced enhancement of plasticity in a monolithic bulk metallic glass at room temperature," Scripta Materialia 59 (2008) 75-78.
Chen, Deformation-induced nanocrystal formation in shear bands of amorphous alloys Nature 367 (1994), 541-543.
Dao, "Toward a quantitative understanding of mechanical behavior of nanocrystalline metals," Acta Materialia 55 (2007), 4041-4065.
Das, "'Work-Hardenable' Ductile Bulk Metallic Glass," Phys. Rev. Lett. 94 (2005) 205501 (4 Pages).
Extended European Search Report dated Dec. 16, 2011 issued in related European Patent Application No. 09812023.1-2122.
Fan, "Ductility of bulk nanocrystalline composites and metallic glasses at room temperature,"Appl. Phys. Lett. 77 (2000) 46-48.
Fan,"Metallic glass matrix composite with precipitated ductile reinforcement," Appl. Phys. Lett. 81 (2002) 1020-1022.
Flores, "Local heating associated with crack tip plasticity in Zr-Ti-Ni-Cu-Be bulk amorphous metals," J. Mater. Res., vol. 14, No. 3, Mar 1999, p. 638-643.
Flores, "Mean Stress Effects on Flow Localization and Failure in a Bulk Metallic Glass," Acta mater. 49 (2001) 2527-2537.
Gleiter, "Nanocrystalline Materials," Prog. Mater. Sci. 33 (1989), 223-315.
Greer, "Bulk Metallic Glasses: At the Cutting Edge of Metals Research," MRS Bulletin 32 (2007), 611.
Hays, "Microstructure Controlled Shear Band Pattern Formation and Enhanced Plasticity of Bulk Metallic Glasses Containing in situ Formed Ductile Phase Dendrite Dispersions," Phys. Rev. Lett. 84 (2000), 2901-2904.
Hofmann, "Designing metallic glass matrix composites with high toughness and tensile ductility," Nature 451 (2008) 1085 (6 pages).
Inoue, "Stabilization of Metallic Supercooled Liquid and Bulk Amorphous Alloys," Acta mater. 48 (2000) 279-306.
International Search Report and Written Opinion dated Nov. 13, 2009 issued in related International Patent Application No. PCT/US09/54942.
Jia, "Effects of Nanocrystalline and Ultrafine Grain Sizes on Constitutive Behavior and Shear Bands in Iron," Acta Mater. 51 (2003), 3495-3509.
Johnson, "Bulk Glass-Forming Metallic Alloys: Science and Technology," MRS Bull. 24 (1999), 42-56.
Kim, "Heterogeneity of a CU47.5Zr47.5Al5 bulk metallic glass" Applied Physics Letters 88, 051911 (2006) (3 Pages).
Kim, "Role of nanometer-scale quasicrystals in improving the mechanical behavior of Ti-based bulk metallic glasses," Appl. Phys. Lett. 83 (2003) 3093-3095.
Kim, "Work hardening ability of ductile Ti45Cu40Ni7.5Zr5Sn2.5 and CU47.5Zr47.5Al5 bulk metallic glasses," Applied Physics Letters 89, 071908 (2006) (3 Pages).
Klement, "Non-crystalline Structure in Solidified Gold-Silicon Alloys," Nature 187 (1960), 869-870.
Lee et al., "Crystallization-induced plasticity of Cu-Zr containing bulk amorphous alloys," Acta Materialia 54 (2006) 349-355.
Lee, "Effect of a controlled volume fraction of dendritic phases on tensile and compressive ductility in La-based metallic glass matrix composites," Acta Materialia 52 (2004) 4121-4131.
Liu, et al., "Super Plastic Bulk Metallic Glasses at Room Temperature," Science vol. 315, Mar. 9, 2007, pp. 1385-1388.
Lu et al., "Ultrahigh strength and high electrical conductivity in copper," Science, vol. 304, Apr. 16, 2004 (p. 422-426).
Saida, "Nanoscale multistep shear band formation by deformation~induced nanocrystallization in Zr-Al-Ni-Pd bulk metallic glass," Applied Physics Letters 87, 151907 (2005).
Saida, "Nanoscale multistep shear band formation by deformation˜induced nanocrystallization in Zr-Al-Ni-Pd bulk metallic glass," Applied Physics Letters 87, 151907 (2005).
Schroers, et al., "Ductile Bulk Metallic Glass," PRL 93, 255506 (2004) (4 Pages).
Steif, "Strain Localization in Amorphous Metals," Acta Metall. 30 (1982), 447-455.
Szuecs, "Mechanical Properties of Zr56.2 Ti13.8 Nb5.0 Cu6.9 Ni5.6 Be12.5 Ductile Phase Reinforced Bulk Metallic Glass Composite," Acta Mater. 49 (2001) 1507-1513.
Valiev, "Institute of Physics of Advanced Materials," Nature Materials vol. 3, Aug. 2004 (p. 511-516).
Wada, "Enhancement of room-temperature plasticity in a bulk metallic glass by finely dispersed porosity," Applied Physics Letters 86, 251907 (2005).
Wang et al., "High tensile ductility in a Nanostructured Metal," Letters to Nature vol. 419, Oct. 31, 2002 (p. 912-915).
Yao, "Superductile bulk metallic glass," Applied Physics Letters 88, 122106 (2006) (3 Pages).
Yavari, "FeNiB-based metallic glasses with fcc crystallisation products," Journal of Non-Crystalline Solids 304 (2002) 44-50.
Yim, "Bulk metallic glass matrix composites," Appl. Phys. Lett. 71 (1997), 3808-3810.
Zhang, "Modulated oscillatory hardening and dynamic recrystallization in cryomilled nanocrystalline Zn," Acta Mater. 50 (2002), 3995-4004.
Zhao,"Simultaneously Increasing the Ductility and Strength of Nanostructured Alloys," Adv. Mater. 18 (2006), 2280 2283.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110108166A1 (en) * 2009-11-06 2011-05-12 The Nanosteel Company, Inc. Utilization of Amorphous Steel Sheets In Honeycomb Structures
US8497027B2 (en) * 2009-11-06 2013-07-30 The Nanosteel Company, Inc. Utilization of amorphous steel sheets in honeycomb structures

Also Published As

Publication number Publication date
CA2735450A1 (en) 2010-03-11
EP2327080A1 (de) 2011-06-01
CA2735450C (en) 2018-02-13
US20120263621A1 (en) 2012-10-18
JP2012500904A (ja) 2012-01-12
KR101629985B1 (ko) 2016-06-13
US20100092329A1 (en) 2010-04-15
JP5728382B2 (ja) 2015-06-03
WO2010027813A1 (en) 2010-03-11
US8679267B2 (en) 2014-03-25
EP2327080A4 (de) 2011-12-28
KR20110069014A (ko) 2011-06-22

Similar Documents

Publication Publication Date Title
US8206520B2 (en) Method of forming ductile metallic glasses in ribbon form
US8317949B2 (en) Ductile metallic glasses
US8882941B2 (en) Mechanism of structural formation for metallic glass based composites with enhanced ductility
Li et al. Influences of oxygen on plastic deformation of a Fe-based bulk metallic glass
US8986472B2 (en) Glassy nano-materials
US20160304998A1 (en) Alloys Exhibiting Spinodal Glass Matrix Microconstituents Structure And Deformation Mechanisms
US8807197B2 (en) Utilization of carbon dioxide and/or carbon monoxide gases in processing metallic glass compositions

Legal Events

Date Code Title Description
AS Assignment

Owner name: THE NANOSTEEL COMPANY, INC.,RHODE ISLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BRANAGAN, DANIEL JAMES;MEACHAM, BRIAN E.;SERGUEEVA, ALLA V.;REEL/FRAME:023491/0055

Effective date: 20090925

Owner name: THE NANOSTEEL COMPANY, INC., RHODE ISLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BRANAGAN, DANIEL JAMES;MEACHAM, BRIAN E.;SERGUEEVA, ALLA V.;REEL/FRAME:023491/0055

Effective date: 20090925

STCF Information on status: patent grant

Free format text: PATENTED CASE

AS Assignment

Owner name: HORIZON TECHNOLOGY FINANCE CORPORATION, CONNECTICUT

Free format text: SECURITY INTEREST;ASSIGNOR:THE NANOSTEEL COMPANY, INC.;REEL/FRAME:035889/0122

Effective date: 20150604

Owner name: HORIZON TECHNOLOGY FINANCE CORPORATION, CONNECTICU

Free format text: SECURITY INTEREST;ASSIGNOR:THE NANOSTEEL COMPANY, INC.;REEL/FRAME:035889/0122

Effective date: 20150604

FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: HORIZON TECHNOLOGY FINANCE CORPORATION, CONNECTICUT

Free format text: SECURITY INTEREST;ASSIGNOR:THE NANOSTEEL COMPANY, INC.;REEL/FRAME:047713/0163

Effective date: 20181127

Owner name: HORIZON TECHNOLOGY FINANCE CORPORATION, CONNECTICU

Free format text: SECURITY INTEREST;ASSIGNOR:THE NANOSTEEL COMPANY, INC.;REEL/FRAME:047713/0163

Effective date: 20181127

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YR, SMALL ENTITY (ORIGINAL EVENT CODE: M2552); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY